Azo dyes with a diazo component of the 3-amino thiophene series and a coupling component of the pyridine, pyridone or pyrazole series

ABSTRACT

Thien-3-ylazo dyes of the formula: ##STR1## where X is cyano, nitro, C 1  -C 6  -alkanoyl, substituted or unsubstituted benzoyl, substituted or unsubstituted phenyl or the radical COOR 1  or CONR 1  R 2  where R 1  and R 2  are identical or different and each is independently of each other substituted or unsubstituted C 1  -C 8  -alkyl, C 5  -C 7  -cycloalkyl, C 3  -C 4  -alkenyl, substituted or unsubstituted phenyl or together with the nitrogen atom linking them a 5- or 6-membered saturated heterocyclic radical, and R 2  may additionally be hydrogen, Y is hydrogen, cyano, C 1  -C 6  -alkanoyl, substituted or unsubstituted benzoyl, C 1  -C 4  -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, substituted or unsubstituted phenyl or the radical COOR 1  or CONR 1  R 2  where R 1  and R 2  are each as defined above, Z is hydrogen, substituted or unsubstituted C 1  -C 8  -alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 1  -C 6  -alkylthio, substituted or unsubstituted phenylthio, substituted or unsubstituted C 1  -C 6  -alkylsulfonyl or phenylsulfonyl or together with the radical Y a fused benzo ring which may be substituted, and K is the radical of a coupling component of the 2,6-diaminopyridine, 6-hydroxypyrid-2-one or 5-aminopyrazole series, are used for dyeing synthetic fiber materials, in particular synthetic polyesters, in yellow to red shades and are notable for good light fastness, fastness to dry heat setting and pleating and for good affinity.

The present invention relates to novel thien-3-ylazo dyes whose couplingcomponents are derived from the pyridine, pyridone or pyrazole seriesand to the use of these dyes for dyeing synthetic fiber materials.

GB-A-2,011,937, DD-A-157,911 and JP-A-226,556/1985 disclosethien-3-ylazo dyes. Furthermore, DE-A-2,441,524 describesbenzothien-3-ylazo dyes, including a case where the coupling componentis 3-cyano-4-methyl-6-hydroxypyrid-2-one. However, it has been foundthat the known dyes have application defects.

It is an object of the present invention to provide new azo dyes whosediazo components are derived from 3-aminothiophene derivatives and whichhave a favorable range of application properties.

We have found that this object is achieved with novel thien-3-ylazo dyesof the formula I ##STR2## where

X is cyano, nitro, C₁ -C₆ -alkanoyl, substituted or unsubstitutedbenzoyl, substituted or unsubstituted phenyl or the radical COOR¹ orCONR¹ R² where R¹ and R² are identical or different and each isindependently of each other substituted or unsubstituted C₁ -C₈ -alkyl,C₅ -C₇ -cycloalkyl, C₃ -C₄ -alkenyl, substituted or unsubstituted phenylor together with the nitrogen atom linking them a 5- or 6- memberedsaturated heterocyclic radical, and R² may additionally be hydrogen,

Y is hydrogen, cyano, C₁ -C₆ -alkanoyl, substituted or unsubstitutedbenzoyl, C₁ -C₄ -alkylsulfonyl, substituted or unsubstitutedphenylsulfonyl, substituted or unsubstituted phenyl or the radical COOR¹or CONR¹ R² where R¹ and R² are each as defined above,

Z is hydrogen, substituted or unsubstituted C₁ -C₈ -alkyl, substitutedor unsubstituted phenyl, substituted or unsubstituted C₁ -C₆ -alkylthio,substituted or unsubstituted phenylthio, substituted or unsubstituted C₁-C₆ -alkylsulfonyl or phenylsulfonyl or together with the radical Y afused benzo ring which may be substituted, and

K is the radical of a coupling component of the pyridine, pyridone orpyrazole series.

All the alkyl groups appearing in the abovementioned formula I can beeither straight-chain or branched.

If substituted phenyl radicals appear in the abovementioned formula I,suitable substituents are for example C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,cyano, fluorine, chlorine, bromine and nitro.

If substituted alkyl radicals appear in the above-mentioned formula I,suitable substituents are for example, unless otherwise stated,hydroxyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₄ -alkoxycarbonyl, cyano andphenyl.

If in the abovementioned formula I the radicals Y and Z together are asubstituted fused benzo ring, suitable substituents are for example C₁-C₄ -alkyl, in particular methyl, cyano, chlorine, bromine and nitro.

If the substituents X and/or Y are each COOR¹ or CONR¹ R², theindividual radicals R¹ and R² are each for example hydrogen (not in thecase of R¹), methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl,heptyl, octyl, 2-ethylhexyl, 2-hydroxyethyl, 2-hydroxypropyl,3-hydroxypropyl, 4-hydroxybutyl, 2-methoxyethyl, 2-ethoxyethyl,2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 3-methoxypropyl,3-ethoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 2-phenoxyethyl,2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl,2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2- or3-butoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl,2-cyanoethyl, 2- or 3-cyanopropyl, 4-cyanobutyl, benzyl, 1- or2-phenylethyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl,2-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl,4-butylphenyl, 4-(2-ethylhexyl)phenyl, 2,4-dimethylphenyl,2,4,6-trimethylphenyl, 4-cyanophenyl, 4-chlorophenyl,2,4-dichlorophenyl, 2-bromophenyl, 3-nitrophenyl, 4-nitrophenyl,prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl or but-3-en-1-yl.

If R¹ and R² together with the nitrogen atom linking them are a 5- or6-membered saturated heterocyclic radical, the possibilities are forexample the following radicals: pyrrolidino, piperidino, morpholino,piperazino or N-(C₁ -C₄ -alkyl)piperazino, such as N-methyl- orN-ethyl-piperazino.

Further radicals X and Y are for example phenyl, 4-nitrophenyl,4-cyanophenyl, 4-methylphenyl, 4-chlorophenyl, 2,4-dichlorophenyl,formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl,benzoyl, 2methylbenzoyl, 4-methylbenzoyl, 4-ethylbenzoyl,4-butylbenzoyl, 4-(2-ethylhexyl)benzoyl, 2,4-dimethylbenzoyl,4-cyanobenzoyl, 4-chlorobenzoyl, 2-bromobenzoyl, 2,4-dichlorobenzoyl or3- or 4-nitrobenzoyl.

Further radicals Y are for example methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl,phenylsulfonyl, 2-methylphenylsulfonyl, 4-methylphenylsulfonyl,4-chlorophenylsulfonyl or 4-bromophenylsulfonyl.

Radicals Z are for example methylthio, ethylthio, propylthio,isopropylthio, butylthio, isobutylthio, secbutylthio, pentylthio,isopentylthio, neopentylthio, tert-pentylthio, hexylthio,2-hydroxyethylthio, 2-methoxyethylthio, 2-ethoxyethylthio,3-methoxypropylthio, 2-phenoxyethylthio, 2- or 3-phenoxypropylthio,methoxycarbonylmethylthio, ethoxycarbonylmethylthio,propoxycarbonylmethylthio, isopropoxycarbonylmethylthio,butoxycarbonylmethylthio, isobutoxycarbonylmethylthio, cyanomethylthio,benzylthio, phenylthio, 2-methylphenylthio, 4-methylphenylthio,4-chlorophenylthio, methylsulfonyl, ethylsulfonyl, propylsulfonyl,isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, pentylsulfonyl,isopentylsulfonyl, hexylsulfonyl, 2-hydroxyethylsulfonyl,2-methoxyethylsulfonyl, 2-ethoxyethylsulfonyl, 2-phenoxyethylsulfonyl,2-methoxycarbonylethylsulfonyl, 2-ethoxycarbonylethylsulfonyl,2-cyanoethylsulfonyl or benzylsulfonyl.

If Z is substituted or unsubstituted C₁ -C₈ -alkyl or substituted orunsubstituted phenyl, reference may be made to the radicals listed byway of example under R¹ and R².

If Y and Z together form a fused benzo ring which may be substituted,for example the following azo dyes ##STR3## where X and K are each asdefined above, come into consideration.

In the formula I, K is the radical of a coupling component KH from thepyridone, pyridine or pyrazole series. Preferably this couplingcomponent KH comes from the 2,6-diaminopyridine, 6-hydroxypyrid-2-one or5-aminopyrazole series.

More particularly, it conforms to formula II, III or IV ##STR4## where

B¹ and B² are identical or different and each is independently of theother hydrogen, C₁ -C₁₂ -alkyl which is substituted and/or interruptedby one or two oxygen atoms, C₅ -C₇ -cycloalkyl, substituted orunsubstituted phenyl, C₃ -C₆ -alkenyl, substituted or unsubstitutedbenzoyl, C₁ -C₈ -alkanoyl, C₁ -C₆ -alkylsulfonyl or phenylsulfonyl,

T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl,

T² is hydrogen, cyano, nitro, carbamoyl, C₁ -C₄ -monoalkyl- or-dialkyl-carbamoyl, C₁ -C₈ -alkanoyl, C₁ -C₆ -alkoxycarbonyl whose alkylchain may be interrupted by one or two oxygen atoms, and

T³ is hydrogen, C₁ -C₁₂ -alkyl which may be substituted and/orinterrupted by one or two oxygen atoms, C₅ -C₇ -cycloalkyl, C₃ -C₆-alkenyl or substituted or unsubstituted phenyl.

If the radicals B¹, B² and/or T³ are each substituted C₁ -C₁₂ -alkylwhich may be interrupted by one or two oxygen atoms, suitablesubstituents are for example phenyl, cyano, C.sub. 1 -C₈-alkoxycarbonyl, phenoxycarbonyl, halogen, in particular chlorine orbromine, hydroxyl, C₁ -C₈ -alkanoyloxy, benzoyloxy, C₅ -C₇ -cycloalkoxyand phenoxy.

Radicals T² are for example mono- or dimethylcarbamoyl, mono- ordiethylcarbamoyl, mono- or dipropylcarbamoyl, mono- ordiisopropylcarbamoyl, mono- or dibutylcarbamoyl, mono- ordiisobutylcarbamoyl, N-methyl-N-ethylcarbamoyl, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl,hexyloxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl,2-propoxyethoxycarbonyl, 2- or 3-methoxypropoxycarbonyl, 2- or3-ethoxypropoxycarbonyl, 4-methoxybutoxycarbonyl or4-ethoxybutoxycarbonyl.

Radicals B¹, B², T¹ and T³ are each for example methyl, ethyl, propyl,isopropyl, butyl, isobutyl or secbutyl.

Radicals B¹, B² and T³ are each further for example, pentyl, isopentyl,neopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl,nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl (the designationsisooctyl, isononyl and isodecyl are trivial names and come from thealcohols obtained by the oxo process - cf. Ullmanns Enzyklopadie dertechnischen Chemie, 4th edition, volume 7, pages 215 to 217, and alsovolume 11, pages 435 and 436), 2-methoxyethyl, 2-ethoxyethyl,2-propoxyethyl, 2-butoxyethyl, 2-(2-ethylhexyloxy)ethyl,2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl,3-(2-ethylhexyloxy)propyl, 2-methoxybutyl, 4-methoxybutyl,2-ethoxybutyl, 4-ethoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,7-dioxaoctyl, 4,7-dioxanonyl, 3,6-dioxadecyl, 4,9-dioxatridecyl,benzyl, 1- or 2-phenylethyl, 8-phenyl-4,7-dioxaoctyl, 2-cyanoethyl,3-cyanopropyl, 4-cyanobutyl, 5-cyano-3-oxapentyl, 6-cyano-4-oxahexyl,8-cyano-4-oxahexyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl,2,3-dihydroxypropyl, 2-hydroxybutyl, 4-hydroxybutyl,5-hydroxy-3-oxapentyl, 6-hydroxy-4-oxahexyl, 8-hydroxy-4-oxaoctyl,8-hydroxy-3,6-dioxaoctyl, 2-phenyl-2-hydroxyethyl, 2-chloroethyl,2-bromoethyl, 2-phenoxyethyl, 3-phenoxypropyl, 4-phenoxybutyl,5-phenoxy-3-oxapentyl, 6-phenoxy-4-oxahexyl, 8-phenoxy-4-oxaoctyl,2-cyclohexyloxyethyl, 3-cyclohexyloxypropyl, 4-cyclohexyloxybutyl,5-cyclohexyloxy-3-oxapentyl, 6-cyclohexyloxy-4-oxahexyl,8-cyclohexyloxy-4-oxaoctyl, 2-methoxycarbonylethyl,2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl,4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl,5-methoxycarbonyl-3-oxapentyl, 6-methoxycarbonyl-4-oxahexyl,8-methoxycarbonyl-4-oxaoctyl, 2-phenoxycarbonylethyl, 2- or3-phenoxycarbonylpropyl, 4-phenoxycarbonylbutyl,5-phenoxycarbonyl-3-oxapentyl, 6-phenoxycarbonyl-4-oxahexyl,8-phenoxycarbonyl-4-oxaoctyl, 2-formyloxyethyl, 2-acetyloxyethyl,2-propionyloxyethyl, 2-butyryloxyethyl, 2-(2-ethylhexanoyloxy)ethyl, 2-or 3-acetyloxypropyl, 2- or 3-propionyloxypropyl, 2- or3-(2-ethylhexanoyloxy)-propyl, 4-acetyloxybutyl, 4-propionyloxybutyl,4-(2-ethylhexanoyloxy)-butyl, 5-acetyl-oxy-3-oxapentyl,5-propionyloxy-3-oxapentyl, 5-(2-ethylhexanoyloxy)-3-oxapentyl,6-acetyloxy-4-oxahexyl, 6-propionyloxy-4-oxahexyl,6-(2-ethylhexanoyloxy)-4-oxahexyl, 8-acetyloxy-4-oxaoctyl,8-propionyloxy-4-oxaoctyl, 8-(2-ethylhexanoyloxy)-4-oxaoctyl,2-benzoyloxyethyl, 2- or 3-benzoyloxypropyl, 4-benzoyloxybutyl,5-benzoyloxy-3-oxapentyl, 6-benzoyloxy-4-oxahexyl,8-benzoyloxy-4-oxaoctyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl,2-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 4-isopropylphenyl,2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-ethoxyphenyl,2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-bromophenyl, allylor methallyl.

Radicals B¹, B² and T² are each further for example formyl, acetyl,propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoylor 2-ethylhexanoyl.

Radicals B¹ and B² are each further for example benzoyl,2-chlorobenzoyl, 4-chlorobenzoyl, 4-bromobenzoyl, 4-methylbenzoyl,4-methoxybenzoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl,isopropylsulfonyl, butylsulfonyl, pentylsulfonyl or hexylsulfonyl.

Preference is given to thien-3-ylazo dyes of the formula I where

X is cyano, nitro, C₁ -C₂ -alkanoyl, benzoyl or the radical COOR¹ whereR¹ is as defined above,

Y is hydrogen, cyano, C₁ -C₄ -alkanoyl, phenyl or the radical COOR¹where R¹ is as defined above,

Z is C₁ -C₄ -alkyl, benzyl, phenyl, C₁ -C₄ -alkylthio, phenylthio or C₁-C₄ -alkylsulfonyl which may each be substituted by cyano, C₁ -C₄-alkoxycarbonyl, methoxy, chlorine or bromine, or phenylsulfonyl ortogether with the radical Y is a fused benzo ring which may besubstituted, and

K is the radical of a coupling component of the 2,6-diaminopyridine,6-hydroxypyrid-2-one or 5-aminopyrazole series.

Particular preference is given to thien-3-ylazo dyes of the formula Iwhere

X is cyano, C₁ -C₄ -alkanoyl or the radical COOR¹ where R¹ is C¹ -C⁴-alkyl or phenyl,

Y is hydrogen, cyano, C₁ -C₄ -alkanoyl, phenyl or the radical COOR¹where R¹ is C₁ -C₄ -alkyl or phenyl,

Z is C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio or C₁ -C₄ -alkylsulfonyl, whichmay each be substituted by cyano, C₁ -C₄ -alkoxycarbonyl, methoxy,chlorine or bromine, or is benzyl, phenyl, phenylthio or phenylsulfonyl,

K is the radical of a coupling component of the 2,6-diaminopyridine,6-hydroxypyrid-2-one or 5-aminopyrazole series.

There may be mentioned in particular thien-3-ylazo dyes of the formulaV, VI or VII ##STR5## where

X is cyano, C₁ -C₄ -alkanoyl or the radical COOR¹ where R¹ is C₁ -C₄-alkyl or phenyl,

Y is hydrogen, cyano, C₁ -C₄ -alkanoyl, phenyl or the radical COOR¹where R¹ is C₁ -C₄ -alkyl or phenyl,

Z is C₁ -C₄ -alkyl or C₁ -C₄ -alkylthio, which may each be substitutedby cyano, C₁ -C₄ -alkoxycarbonyl, methoxy, chlorine or bromine, or isbenzyl, phenyl, phenylthio, C₁ -C₄ -alkylsulfonyl or phenylsulfonyl, and

T² is hydrogen, cyano, carbamoyl or C₁ -C₄ -alkoxycarbonyl and B¹, B²,T¹ and T³ are each as defined above.

Industrially particularly useful thien-3-ylazo dyes are of the formulaV, VI or VII where

X is cyano or the radical COOR¹ where R¹ is C₁ -C₄ -alkyl,

Y is cyano, phenyl or the radical COOR¹ where R¹ is C₁ -C₄ -alkyl,

Z is phenyl or unsubstituted or cyano- or C₁ -C₄-alkoxycarbonyl-substituted C₁ -C₄ -alkyl,

T¹ is hydrogen, methyl or phenyl,

T² is hydrogen, cyano or C₁ -C₄ -alkoxycarbonyl and B¹, B² and T³ areeach as defined above.

To prepare the thien-3-ylazo dyes of the formula I according to theinvention, a conventionally obtainable diazonium compound of an amine ofthe formula VIII ##STR6## where X, Y and Z are each as defined above,may be reacted with a coupling component HK as described above in aconventional manner.

Further details of the preparation may be found in the examples.

3-Aminothiophenes of the formula VIII are known and described forexample in Liebigs Ann. Chem. 656 (1962), 90; Pharm. Zentralhalle 107(1968), 348; GB-A-2,011,937; or Synthesis 1982, 1056. Furtherinformation about ways of synthesizing 3-aminothiophenes is given inHeterocyclic Compounds, vol. 44, John Wiley & Sons, Inc., 1986,Thiophene and its Derivatives, parts 1 and 2.

The dyes according to the invention are yellow to red and are notablefor good light fastness, fastness to dry heat setting and pleating andfor good affinity. They are suitable for dyeing synthetic fibermaterials, such as polyamides, cellulose esters or blends of polyestersand cellulose fibers. But particularly, they are suitable for dyeingsynthetic polyesters.

The Examples which now follow serve to illustrate the invention in moredetail. Percentages are by weight, unless otherwise stated.

EXAMPLE 1

4.9 g of 3-amino-4-cyano-2-methoxycarbonyl-5-methylthiophene were addedto 37.5 ml of 17:3 glacial acetic acid/propionic acid. 10 ml of 85%strength sulfuric acid were added dropwise at 10°-20° C., followed at0°-5° C. by 4.3 ml of nitrosylsulfuric acid (11.5% of N₂ O₃), and themixture was stirred at 0° -5° C. for 4 hours.

The diazonium salt solution prepared above was added dropwise to 6.6 gof 2,6-bis(2-methoxyethylamino)-3-cyano-4-methylpyridine dissolved in 20ml of N,N-dimethylformamide, 20 ml of dilute hydrochloric acid, 100 g ofice and 0.5 g of sulfamic acid at 0° C. The mixture was stirred at 0°-5°C. for 4 hours, slowly warmed to room temperature and filtered withsuction, and the precipitate was washed and dried.

Yield: 10.5 g of the dye of the formula ##STR7## which dyes polyestermaterial in fast orange shades.

λ_(max) (CH₂ CL₂): 485 nm.

EXAMPLE 2

The diazonium salt solution prepared in Example 1 was added dropwisewith stirring to 5.85 g of 3-cyano-6-hydroxy-1-hexyl-4-methylpyrid-2-onedissolved in 20 ml of N,N-dimethylformamide, 20 ml of dilutehydrochloric acid, 100 g of ice and 0.5 g of sulfamic acid at 0° -3° C.After 4 hours at 0° -5° C. and warming to room temperature, theprecipitate was filtered off with suction, washed and dried to leave10.3 g of the dye of the formula ##STR8## which dyes polyester fibermaterial in fast yellow shades.

λ_(max) (CH₂ CL₂): 431 nm.

EXAMPLE 3

4.9 g of 3-amino-2,4-dicyano-5-methylthiothiophene were suspended in 50ml of 3:1 glacial acetic acid/propionic acid. 8.2 g of nitrosylsulfuricacid (11.5% of N₂ O₃) were added dropwise at 0°-59° C., and the mixturewas stirred at 0° -5° C. for 3 hours.

This diazonium salt solution was added dropwise to 7.7 g of2,6-bis(3-methoxypropylamino)-3-cyano-4-methylpyridine dissolved in 100ml of N,N-dimethylformamide, 0.5 g of sulfamic acid and 100 g of ice at0°-5° C. in the course of 20 minutes. The mixture was stirred at 0°-5°C. for 4 hours and at room temperature for 8 hours. The dye product wasfiltered off with suction, washed and dried. Yield: 6.2 g of the dye ofthe formula ##STR9## which dyes polyester material in fast orangeshades.

λ_(max) (CH₂ CL₂): 491 nm.

EXAMPLE 4

5.5 g of 3-amino-2-cyano-5-nitrobenzothiophene were diazotized asdescribed in Example 1 and added dropwise to a solution of 6.6 g of2,6-bis(2-methoxyethylamino)-3-cyano-4-methylpyridine in 20 ml ofN,N-dimethylformamide, 100 ml of water, 20 ml of hydrochloric acid, 100g of ice and 0.5 g of sulfamic acid with stirring at 0°-5° C. Workingupas described in Example 1 left 10.4 g of the dye of the ##STR10## whichdyes polyester in fast yellowish red shades.

λ_(max) (CH₂ CL₂): 506 nm

The same method was used to obtain the dyes listed in the followingtables 1 to 4:

                                      TABLE 1                                     __________________________________________________________________________     ##STR11##                                                                                                                      Hue on                      Ex.                                                                              X     Y     Z     R.sup.1    R.sup.2        R.sup.3                                                                          PES                         __________________________________________________________________________     5 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub                                    .3             H  orange                       6 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub                                    .3             H  orange                       7 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCOCH.sub                                    .3             H  orange                       8 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            H          (1)            H  orange                       9 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub. 4 H.sub.8                                             OCOC.sub.2 H.sub.5                                                                           H  orange                      10 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            H          (2)            H  orange                      11 CO.sub.2 CH.sub.3                                                                   CN    C.sub.2 H.sub.5                                                                     H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub                                    .3             H  orange                      12 CN    CN    CH.sub.3                                                                            H          (2)            H  orange                      13 CN    CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                    1              H  orange                      14 COCH.sub.3                                                                          CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                     H.sub.5        H  orange                      15 COC.sub.6 H.sub.5                                                                   CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                     H.sub.9        H  orange                      16 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2                                     H.sub.5        H  orange                      17 CO.sub.2 C.sub.2 H.sub.5                                                            CO.sub.2 C.sub.2 H.sub.5                                                            CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4                                     H.sub.9        H  orange                      18 CO.sub.2 CH.sub.3                                                                   CO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                     H.sub.9        H  orange                      19 CO.sub. 2 CH.sub.3                                                                  CO.sub.2 CH.sub.3                                                                   C.sub.2 H.sub.5                                                                     H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                    O              H  orange                      20 COCH.sub.3                                                                          CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub                                    .3             H  orange                      21 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                          H  orange                      22 CN    CN    CH.sub.3                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub                                    .3             H  orange                      23 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.2 H.sub.4 OCOCH.sub.3                                                              C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                     H.sub.5        H  orange                      24 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.2 H.sub.4 OH                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                     H.sub.5        H  orange                      25 CO.sub.2 CH.sub.3                                                                   CN    C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 OCOCH.sub.3                                                              C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                             H  orange                      26 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                     H.sub.9        H  orange                      27 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                          H  orange                      28 CO.sub.2 CH.sub.3                                                                   H     CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                          H  orange                      29 CO.sub.2 CH.sub.3                                                                   H     CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                    T              H  orange                      30 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCOCH.sub.3                                                               ##STR12##     H  yellowish red               31 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                             ##STR13## C.sub.3 H.sub.6 OCOCH.sub.3                                                                  H  yellowish red               32 CN    CN    CH.sub.3                                                                             ##STR14## C.sub.3 H.sub.6 OCOCH.sub.3                                                                  H  red                         33 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                       ##STR15##     H  orange                      34 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OH                                                                        ##STR16##     H  yellowish red               35 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OH                                                                        ##STR17##     H  red                         36 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                ##STR18##     H  red                         37 CO.sub.2 CH.sub.3                                                                   CO.sub.2 CH.sub.3                                                                   C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OCH.sub.3                                                                    H  orange                      38 CO.sub.2 C.sub.2 H.sub.5                                                            CN    C.sub.4 H.sub.9                                                                     C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                                                                    H  orange                      39 COCH.sub.3                                                                          CN    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.                                    2 H.sub.5      H  orange                      40 COC.sub.6 H.sub.5                                                                   CN    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                     H.sub.9        H  orange                      41 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OH                                                          H  orange                      42 CO.sub.2 CH.sub.3                                                                   H     CH.sub.3                                                                            C.sub.3 H.sub.6 OH                                                                        ##STR19##     H  yellowish red               43 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCOCH.sub.3                                                               ##STR20##     H  yellowish red               44 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4                                     H.sub.9        H  orange                      45 COCH.sub.3                                                                          CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OCH.sub.3                                                                    H  orange                      46 CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4                                     H.sub.9        H  orange                      47 CN    CN    CH.sub.3                                                                            H                                                                                         ##STR21##     H  orange                      48 CN    CN    CH.sub.3                                                                            H                                                                                         ##STR22##     H  orange                      49 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            H                                                                                         ##STR23##     H  orange                      50 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            H                                                                                         ##STR24##     H  reddish orange              51 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.                                    2 H.sub.5      H  orange                      52 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                                                                    CH.sub.3                                                                         reddish                                                                       orange                      53 CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                                                  reddish                                                                       orange                      54 CN    CN    SCH.sub.3                                                                           H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub                                    .3             H  orange                      55 CN    CN    SCH.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                          H  orange                      56 CN    CN    SCH.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                                                                    H  orange                      57 CN    CN    SCH.sub.3                                                                           H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2                                     H.sub.5        H  orange                      58 CO.sub.2 CH.sub.3                                                                   CN    (3)   H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 C.sub.2                                      H.sub.5        H  orange                      59 CO.sub.2 CH.sub.3                                                                   CN    (3)   C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                                                                    H  orange                      60 CO.sub.2 CH.sub.3                                                                   C.sub.6 H.sub.5                                                                     (3)   H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                    O              H  orange                      61 NO.sub.2                                                                            CN    SCH.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                                                                    H  reddish                                                                       orange                      62 CN    CN    SO.sub.2 CH.sub.3                                                                   C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                                                                    H  orange                      63 CO.sub.2 CH.sub.3                                                                   CN    SCH.sub.3                                                                           H          C.sub.3 H.sub.4 OC.sub.4 H.sub.8 OC.sub.2                                     H.sub.5        H  orange                      64 CO.sub.2 CH.sub.3                                                                   CN    SCH.sub.3                                                                           C.sub.2 H.sub.4 OH                                                                       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                          H  orange                      __________________________________________________________________________     ##STR25##                                                                     (2) C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.2 CH(CH.sub.3).sub.2      

                                      TABLE 2                                     __________________________________________________________________________     ##STR26##                                                                                                            Hue on                                Ex.                                                                              X    Y    Z       R           W      PES                                   __________________________________________________________________________    65 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              CH.sub.3    CN     yellow                                66 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              C.sub.4 H.sub.9                                                                           CN     yellow                                67 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                               ##STR27##  CN     yellow                                68 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         CN     yellow                                69 CN   CN   CH.sub.3                                                                              C.sub.6 H.sub.13                                                                          CN     yellow                                70 CN   CN   CH.sub.3                                                                               ##STR28##  CN     yellow                                71 CN   CN   CH.sub.3                                                                              C.sub.3 H.sub.7                                                                           CN     yellow                                72 COCH.sub.3                                                                         CN   CH.sub.3                                                                              CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                               CN     yellow                                73 COCH.sub.3                                                                         CN   CH.sub.3                                                                              CH.sub.3    CN     yellow                                74 COCH.sub.3                                                                         CN   CH.sub.3                                                                               ##STR29##  CN     yellow                                75 COC.sub.6 H.sub.5                                                                  CN   CH.sub.3                                                                               ##STR30##  CN     yellow                                76 COC.sub.6 H.sub.5                                                                  CN   CH.sub.3                                                                              C.sub.4 H.sub.9                                                                           CN     yellow                                77 CO.sub.2 C.sub.2 H.sub.5                                                           CN   CH.sub.3                                                                              CH.sub.3    CN     yellow                                78 CO.sub.2 C.sub.2 H.sub.5                                                           CO.sub.2 C.sub.2 H.sub.5                                                           CH.sub.3                                                                              CH.sub.3    CN     yellow                                79 CO.sub.2 CH.sub.3                                                                  H    CH.sub.3                                                                              C.sub.4 H.sub.9                                                                           CN     yellow                                80 CO.sub.2 CH.sub.3                                                                  CO.sub.2 CH.sub.3                                                                  CH.sub.3                                                                               ##STR31##  CN     yellow                                81 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              CH.sub.3    CONH.sub.2                                                                           yellow                                82 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                               CONH.sub.2                                                                           yellow                                83 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              C.sub.3 H.sub.78                                                                          CONHC.sub.3 H.sub.7                                                                  yellow                                84 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              C.sub.3 H.sub.6 OC.sub.2 H.sub.9 OC.sub.6 H.sub.5                                         H      yellow                                85 CO.sub.2 CH.sub.3                                                                  CN   CH.sub.3                                                                              C.sub.4 H.sub.9                                                                           CO.sub.2 C.sub.2 H.sub.5                                                             yellow                                86 CO.sub.2 C.sub.2 H.sub.5                                                           CN   CH.sub.3                                                                              C.sub.6 H.sub.13                                                                          CONH.sub.2                                                                           yellow                                87 CN   CN   CH.sub.3                                                                              C.sub.6 H.sub.13                                                                          CONH.sub.2                                                                           yellow                                88 CN   CN   SCH.sub.3                                                                             CH.sub.3    CN     yellow                                89 CN   CN   SCH.sub.3                                                                             C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                                 CN     yellow                                90 CN   CN   SCH.sub.3                                                                             C.sub.4 H.sub.9                                                                           CN     yellow                                91 CO.sub.2 CH.sub.3                                                                  CN   SCH.sub.2 CO.sub.2 CH.sub.3                                                           C.sub.4 H.sub.9                                                                           CN     yellow                                92 CO.sub.2 CH.sub.3                                                                  C.sub.6 H.sub.5                                                                    SCH.sub.2 CO.sub.2 CH.sub.3                                                           C.sub.4 H.sub.9                                                                           CN     yellow                                93 CO.sub.2 CH.sub.3                                                                  CN   SCH.sub.3                                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         CN     yellow                                __________________________________________________________________________     (3) SCH.sub.2 CO.sub.2 CH.sub.3 -                                        

                                      TABLE 3                                     __________________________________________________________________________     ##STR32##                                                                                                        Hue on                                    Ex.                                                                              X     Y     Z        T.sup.1                                                                           T.sup.3 PES                                       __________________________________________________________________________     94                                                                              CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3 H   CH.sub.2 C.sub.6 H.sub.5                                                              yellow                                     95                                                                              CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3 H   C.sub.6 H.sub.5                                                                       yellow                                     96                                                                              CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3 H                                                                                  ##STR33##                                                                            yellow                                     97                                                                              CO.sub.2 CH.sub.3                                                                   CN    CH.sub.3 CH.sub.3                                                                          C.sub.6 H.sub.5                                                                       yellow                                     98                                                                              CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3 H   CH.sub.2 C.sub.6 H.sub.5                                                              yellow                                     99                                                                              CO.sub.2 C.sub.2 H.sub.5                                                            CN    CH.sub.3 H   CH.sub.3                                                                              yellow                                    100                                                                              COCH.sub.3                                                                          CN    CH.sub.3 H   C.sub. 6 H.sub.5                                                                      yellow                                    101                                                                              CN    CN    CH.sub.3 H                                                                                  ##STR34##                                                                            yellow                                    102                                                                              CO.sub.2 CH.sub.3                                                                   CO.sub.2 CH.sub.3                                                                   CH.sub.3 H   CH.sub.2 C.sub.6 H.sub.5                                                              yellow                                    103                                                                              CO.sub.2 CH.sub.3                                                                   CO.sub.2 CH.sub.3                                                                   C.sub.2 H.sub.5                                                                        H   CH.sub.2 C.sub.6 H.sub.5                                                              yellow                                    104                                                                              CO.sub.2 CH.sub.3                                                                   H     CH.sub.3 H   C.sub.6 H.sub.5                                                                       yellow                                    105                                                                              COC.sub.6 H.sub.5                                                                   CN    CH.sub.3 H                                                                                  ##STR35##                                                                            yellow                                    106                                                                              CN    CN    SCH.sub.3                                                                              H                                                                                  ##STR36##                                                                            yellow                                    107                                                                              CN    CN    SCH.sub.3                                                                              H   CH.sub.2 C.sub.6 H.sub.5                                                              yellow                                    108                                                                              CO.sub.2 CH.sub.3                                                                   CN    SCH.sub.2 CO.sub.2 CH.sub.3                                                            H   CH.sub.2 C.sub.6 H.sub.5                                                              yellow                                    109                                                                              CO.sub.2 CH.sub.3                                                                   CN    SCH.sub.3                                                                              H   C.sub.6 H.sub.5                                                                       yellow                                    110                                                                              CO.sub.2 CH.sub.3                                                                   C.sub.6 H.sub.5                                                                     SCH.sub.2 CO.sub.2 CH.sub.3                                                            H                                                                                  ##STR37##                                                                            yellow                                    __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    DNNK                                                                                                                              Hue on                    Ex.                                                                              D                        K                       PES                       __________________________________________________________________________    111                                                                               ##STR38##                                                                                              ##STR39##              yellowish red             112                                                                               ##STR40##                                                                                              ##STR41##              yellowish red             113                                                                               ##STR42##                                                                                              ##STR43##              yellowish red             114                                                                               ##STR44##                                                                                              ##STR45##              yellowish red             115                                                                               ##STR46##                                                                                              ##STR47##              yellow                    116                                                                               ##STR48##                                                                                              ##STR49##              yellow                    117                                                                               ##STR50##                                                                                              ##STR51##              yellow                    118                                                                               ##STR52##                                                                                              ##STR53##              yellow                    119                                                                               ##STR54##                                                                                              ##STR55##              yellow                    120                                                                               ##STR56##                                                                                              ##STR57##              yellow                    121                                                                               ##STR58##                                                                                              ##STR59##              yellow                    122                                                                               ##STR60##                                                                                              ##STR61##              yellow                    123                                                                               ##STR62##                                                                                              ##STR63##              yellowish red             __________________________________________________________________________

We claim:
 1. A thien- 3-ylazo dye of the formula I ##STR64## where X iscyano, C₁ -C₆ -alkanoyl, substituted or unsubstituted benzoyl,substituted or unsubstituted phenyl or the radical COOR¹ or CONR¹ R²where R¹ and R² are identical or different and each is independently ofeach other, substituted or unsubstituted C₁ -C₈ -alkyl, C₅ -C₇-cycloalkyl, C₃ -C₄ -alkenyl, substituted or unsubstituted phenyl ortogether with the nitrogen atom linking them a member selected from thegroup consisting of pyrrolidino, piperidino, morpholino, piperazino andN-(C₁ -C₄ -alkyl)piperazino, and R² may additionally be hydrogen,Y ishydrogen, cyano, C₁ -C₆ -alkanoyl, substituted or unsubstituted benzoyl,substituted or unsubstituted phenyl or the radical COOR¹ or CONR¹ R²where R¹ and R² are each as defined above, Z is hydrogen, substituted orunsubstituted C₁ -C₈ -alkyl, substituted or unsubstituted C₁ -C₆-alkylthio, substituted or unsubstituted phenyl, substituted orunsubstituted phenylthio or substituted or unsubstituted C₁ -C₆-alkylsulfonyl or phenylsulfonyl and K is a group of the formula (II)##STR65## where B¹ and B² are identical or different and each isindependently of the other hydrogen, unsubstituted or substituted C₁-C₁₂ -alkyl, substituted or unsubstituted C₃ -C₁₂ -alkoxyalkoxyalkyl orC₂ -C₁₂ -alkoxyalkyl, C₅ -C₇ -cycloalkyl, substituted or unsubstitutedphenyl, C₃ -C₆ -alkenyl, substituted or unsubstituted benzoyl, C₁ -C₈-alkanoyl, C₁ -C₆ -alkylsulfonyl or phenylsulfonyl, T¹ is hydrogen, C₁-C₄ -alkyl or phenyl, T² is hydrogen, cyano, nitro, carbemoyl, C₁ -C₄-monoalkyl- or dialkyl-carbamoyl, C₁ -C₈ -alkanoyl, C₁ -C₆ -alkanoyl, C₂-C₆ -alkoxycarbonyl or C₃ -C₆ -alkoxyalkoxyalkoxycarbonyl, and thesubstituents on substituted alkyl, alkylthio, alkoxyalkyl,alkoxyalkoxyalkyl or alkylsulfonyl values of X, Y and Z are selectedfrom the group consisting of hydroxy, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₄-alkoxycarbonyl, cyano and phenyl, the substituents on substitutedbenzoyl, phenyl, phenylthio and phenylsulfonyl values of X, Y, Z, B¹ andB² are selected from the group consisting of C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, cyano, fluoro, chloro, bromo and nitro, and the substituents onsubstituted alkyl, alkoxyalkoxyalkyl and alkoxyalkyl values of B¹ and B²are phenyl, cyano, C₁ -C₈ -alkoxycarbonyl, phenoxycarbonyl, halogen,hydroxyl, C₁ -C₈ -alkanoyloxy, benzoyloxy, C₅ -C₇ -cycloalkoxy andphenoxy.
 2. The compound of claim 1 having the formula: ##STR66##
 3. Thecompound of claim 1 having the formula: ##STR67##
 4. The compound ofclaim 1 having the formula: ##STR68##